EP1481995B1 - Aqueous copolymer dispersions, method for their production and coating compositions containing them - Google Patents

Aqueous copolymer dispersions, method for their production and coating compositions containing them Download PDF

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EP1481995B1
EP1481995B1 EP04009362A EP04009362A EP1481995B1 EP 1481995 B1 EP1481995 B1 EP 1481995B1 EP 04009362 A EP04009362 A EP 04009362A EP 04009362 A EP04009362 A EP 04009362A EP 1481995 B1 EP1481995 B1 EP 1481995B1
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monomers
monomer
weight
copolymer dispersion
aqueous copolymer
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German (de)
French (fr)
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EP1481995A1 (en
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Christian Dr. Meiners
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Celanese Sales Germany GmbH
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Celanese Emulsions GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers

Definitions

  • the present invention relates to aqueous copolymer dispersions, processes for their preparation and their use in coating compositions.
  • copolymers are often used, which are crosslinked by the use of functional monomers. If elastic coatings or films are to be produced, their elastic properties are characterized by their expansion and elastic moduli. The elastic moduli of elasticity of the polymers can be adjusted by varying the amount of crosslinker over a wide range.
  • Suitable crosslinkers are either bi- or oligo-olefinically unsaturated monomers, such as, for example, hexanediol dimethacrylate, or functional monomers or metal complexes, which generally lead to crosslinking only during film formation.
  • Suitable metal complexes can be derived from group 4A transition metals of the periodic table, such as zirconium (P.J. Moles, Polym., Paint Color J. 1988, 178, page 154).
  • Crosslinkers which have several ethylenically unsaturated groups lead to a more or less homogeneous crosslinking within the dispersion particles, while adjacent particles are physically crosslinked only by entanglement of polymer chain ends.
  • reactive crosslinking systems are known in which, in addition to crosslinking of the polymer chains in the polymer particles, also to a interparticle crosslinking reaction of adjacent polymer particles in the film formation comes.
  • Typical reactive crosslinker monomers which are incorporated as functional units in the copolymer are N-methylolacrylamide (NMAA) or olefinically unsaturated silanes and epoxides, such as vinyltrimethoxysilane or glycidyl methacrylate.
  • NMAA N-methylolacrylamide
  • epoxides such as vinyltrimethoxysilane or glycidyl methacrylate.
  • Aqueous copolymer dispersions in which monoethylenically unsaturated, crosslinking silanes are copolymerized are known from DE 198 58 851 A1.
  • Preferred silanes are vinyltrimethoxysilane or silanes containing epoxide groups, such as the glycidyl group. Coatings and films based on such copolymer dispersions have an increased elasticity.
  • Database Chemabs., XP002292939 discloses silane couplers for aqueous coating compositions.
  • EP 0 214 696 A1 deals with the subsequent addition of 3-glycidoxypropyltrimethoxysilane to a styrene / butyl acrylate / acrylic acid copolymer.
  • Subsequent modification with epoxysilanes increases the wet tensile stress of such high styrene-based adhesives on ceramic material.
  • US-A-4,077,932 and US-A-4,032,487 are concerned with aqueous adhesive compositions based on copolymers in which nitrogen-containing monomers, such as dimethylaminomethyl methacrylate, are copolymerized.
  • storage-stable dispersions can be obtained by modifying carboxyl-containing polymers with epoxysilanes, for example 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and initiating the crosslinking reaction with the epoxysilane crosslinker prior to use as a coating agent by addition of a catalyst.
  • epoxysilanes for example 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane
  • tertiary amines or organotin compounds are recommended.
  • the known compositions still have a high adhesive capacity even after storage.
  • the known compositions require the presence of catalysts, for example tertiary amines, which in the presence of oxygen may, on prolonged storage, lead to undesired and colored decomposition products. If the catalytic material is added already during preparation of the preparation, its storage stability is reduced.
  • crosslinking systems When crosslinking systems are used in copolymer dispersions, an opposite coupling of elongation at break and tensile stress is generally observed, that is, the tensile stress decreases as the elongation at break increases.
  • crosslinker systems in which the usual antagonistic coupling of elongation at break and tensile stress is eliminated, so at elevated crosslinker concentration in the copolymer an increased tensile stress at constant or increased elongation at break is observed.
  • the present invention relates to aqueous copolymer dispersion obtainable by free-radical polymerization of at least the monomers a) and b) and by subsequent addition of at least one cycloalkylepoxysilane to the resulting copolymer emulsion, wherein monomer a) is an ester of ⁇ , ⁇ -monoethylenic containing 3 to 6 C atoms unsaturated carboxylic acids and alkanols containing 1 to 18 C atoms and optionally a vinylaromatic compound or a mixture of these monomers and wherein monomer b) is a mono- or polybasic ⁇ , ⁇ -monoethylenically unsaturated acid and / or their anhydride.
  • aqueous copolymer dispersion which, in addition to the monomers a) and b), is also derived from at least one of the monomers c), d), e) and / or f), wherein monomer c) is a di- or oligoethylenically unsaturated crosslinking monomer or a mixture of these monomers, monomer d) is an ⁇ , ⁇ -monoethylenically unsaturated carboxylic acid containing 3 to 8 C atoms or a mixture of these monomers, monomer e) is a reactive crosslinker monomer selected from a combination of at least one ethylenically unsaturated silane with at least one ethylenic unsaturated monomer having an oxirane group or a mixture of these monomers and monomer f) is another copolymerizable ethylenic unsaturated monomer or a mixture of these monomers except a nitrogen-containing epoxy group-reactive monomer
  • the invention relates to the above-defined aqueous copolymer dispersion having a solids content of 20-65% by weight, the copolymer being derived from 40 to 99.8% by weight of monomer a) or mixtures thereof, of 0.1 to 10% by weight of monomer b) or mixtures thereof, from 0 to 10% by weight of monomer c) or mixtures thereof, from 0 to 5% by weight of monomer d) or mixtures thereof, from 0 to 5% by weight to monomer e) or mixtures thereof, and from 0 to 30% by weight of monomer f) or mixtures thereof, the amounts of monomer being based on the total amount of monomer used.
  • a further preferred embodiment of the present invention relates to the above-defined aqueous copolymer dispersions, wherein the weight proportions of the monomers a) and b) are chosen so that a copolymer composed only of these monomers has a glass transition temperature in the range from -50 to 120 ° C, preferably between -50 and 15 ° C would have.
  • the cycloalkylpoxysilane used according to the invention is preferably a compound of the general formula (I) where R 1 , R 2 and R 3 are linear or branched alkoxy radicals with bonding of the oxygen atom to the silicon atom and / or alkyl radicals having 1-10 C atoms and R 4 is a linear or branched alkylene radical having 1-10 C atoms.
  • novel aqueous copolymer dispersions preferably contain one or more UV initiators B) and / or one or more emulsifiers C), and / or one or more water-soluble copolymers D).
  • cycloalkylepoxysilanes of up to 0.5% by weight, in particular of up to 0.25% by weight, based on the aqueous dispersion of the copolymer A), are added.
  • the minimum amount of the Cycloalkylepoxysilanen is 0.05 wt .-%, based on the aqueous dispersion of the copolymer A).
  • R 1 , R 2 and R 3 each independently represent -OCH 3 or -OC 2 H 5 and R 4 -C 2 H 4 -.
  • esters of ⁇ As esters of ⁇ , ⁇ -monoethylenically unsaturated carboxylic acids containing 3 to 6 carbon atoms and alkanols containing 1 to 18 carbon atoms, esters of acrylic and / or methacrylic acid are preferably used.
  • the synergetic increase in the tensile stress and elongation at break mean an improvement in the performance properties of the coatings produced with the novel copolymer dispersions.
  • the resulting increase in the energy required for the film tear causes increased crack bridging at a given acting energy, as occurs, for example, in a crack expansion of a painted house facade.
  • a substantial reduction of the elongation at break in favor of increased tensile stress has a disadvantageous effect here, since the elongation at break is generally directly proportional to the crack bridging capacity.
  • the cohesive energy of polymer films is proportional to the area under the tensile / ultimate elongation curve and can be determined experimentally in tensile elongation tests.
  • the cycloalkylepoxysilanes are added to the aqueous copolymer dispersion A). Their addition is thus carried out after the actual copolymerization of Monomers a) and b), optionally with the monomers c) to f), to the copolymer A). Since only small amounts of Cycloalkylepoxysilanen sufficient as Nachbine, the novel aqueous copolymer dispersions can be produced very inexpensively.
  • copolymers which have a low glass transition temperature in the range from -50 to + 15 ° C. are used in the aqueous copolymer dispersion according to the invention, which makes it possible to dispense with the use of curing catalysts for the cycloalkylepoxysilanes.
  • UV initiators B it is also possible to add UV initiators B), emulsifiers C) and water-soluble copolymers D) as a follow-up to the aqueous copolymer dispersion.
  • the glass transition temperatures of the copolymers are determined by means of DSC (Differential Scanning Calorimetry, 20 ° C./min, midpoint), the monomer compositions of the copolymers characterized by the glass transition temperature are determined by the Fox equation (TG Fox, Bull. Am. Phys. Soc. Ser. II) 1956, 1, 123), taking into account the glass transition temperatures, determined by means of DSC, of the individual monomer homopolymers (as known, for example, from Emulsion Polymerization and Emulsion Polymers, John Wiley, Chichester 1997, page 624).
  • copolymers which contain a reactive crosslinker system comprising at least one ethylenically unsaturated silane, for example vinyltriethoxysilane, and at least one ethylenically unsaturated oxirane derivative, for example glycidyl methacrylate (monomers e), also exhibit the synergistic correlation between tensile stress and elongation at break in coatings according to the invention after having reacted with the cycloalkylepoxysilanes were made up.
  • a reactive crosslinker system comprising at least one ethylenically unsaturated silane, for example vinyltriethoxysilane, and at least one ethylenically unsaturated oxirane derivative, for example glycidyl methacrylate (monomers e)
  • the copolymer A) is composed of the monomers a) and b) and, if appropriate, the monomers c) to f) can each be polymerized in copolymerized form.
  • the monomers a) are preferably esters of (meth) acrylic acid.
  • (meth) acrylic acid refers to both acrylic and methacrylic acid and (meth) acrylate esters of acrylic and methacrylic acid.
  • Preferred vinyl aromatic compounds are styrene, methylstyrene, ethylstyrene, dimethylstyrene, diethylstyrene and trimethylstyrene. Particularly preferred is styrene.
  • monomers b) it is preferred to use (meth) acrylic acid, itaconic acid, fumar and maleic acid and their anhydrides.
  • hemiamides and half esters of ethylenically unsaturated dicarboxylic acids are also suitable as monomers b).
  • Suitable crosslinking monomers c) are especially di- or oligofunctional (meth) acrylic esters, such as 1,6-hexanediol di (meth) acrylate, 1,3- and 1,4-butanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate. Preference is given to amounts between 0 and 0.5% by weight of these monomers, based on the total weight of the monomers.
  • Suitable monomers d) are especially (meth) acrylamide and also 2-acrylamido-2-methylpropanesulfonic acid and its salts.
  • Suitable monomers e) are ethylenically unsaturated silanes having at least one ethylenically unsaturated radical in combination with at least one oxirane group-containing ethylenically unsaturated monomer. Such a combination is also referred to as a reactivation system.
  • copolymerizable silanes of the general formula CH 2 CH-Si (OX) 3 , wherein X is hydrogen, an acyl group and / or an alkyl group having a maximum of 10 carbon atoms.
  • Examples of such silanes are vinyltrimethoxysilane and vinyltriethoxysilane.
  • An example of this monomer group is y-methacryloyl-oxypropyltriethoxysilane.
  • Preferred ethylenically unsaturated oxirane derivative is glycidyl methacrylate and glycidyl acrylate.
  • Other monomers f) used are, for example, copolymerizable emulsifiers and costabilizers, such as poly (alkoxylate) (meth) acrylate phosphates or poly (alkoxylate) (meth) acrylate alcohols or ethers, such as Plex® 6850-0, 2- (2-methylpropenoato) ethylsulfonate or sulfate, vinyl sulfonate and functional monomers such as fluorinated alkyl (meth) acrylates.
  • copolymerizable emulsifiers and costabilizers such as poly (alkoxylate) (meth) acrylate phosphates or poly (alkoxylate) (meth) acrylate alcohols or ethers, such as Plex® 6850-0, 2- (2-methylpropenoato) ethylsulfonate or sulfate, vinyl sulfonate and functional monomers such as fluorinated alkyl (
  • Suitable components B) include benzophenone, acetophenone and, in particular, benzophenone derivatives such as 1-hydroxycyclohexylphenyl ketone and also 4-methylbenzophenone and 2,4,6-trimethylbenzophenone.
  • phosphine oxide derivatives such as 2,4,6-Trimethylbenzoyldiphenylphosphinoxid be used alone or in admixtures with other UV initiators. Suitable photoinitiators can also be used together with light stabilizers.
  • Component B) is incorporated by stirring into the copolymer dispersion containing at least one copolymer A).
  • component B adjuvants may be added which keep the photoinitiator in a liquid state, such as, for example, solvents or crystallization inhibitors. In terms of application, it is particularly advantageous if component B) is liquid, since it is easier to incorporate into the copolymer dispersion.
  • Component B) can be introduced into the copolymer dispersion according to the invention or, alternatively, directly into the coating produced from the copolymer dispersion according to the invention.
  • emulsifiers C such emulsifiers can be added subsequently, which are also used in the emulsion polymerization.
  • nonionic emulsifiers for example fatty alcohol polyalkoxylate ethers such as ethoxylation of lauryl, oleyl or stearyl and coconut fatty alcohol, ethoxylated polypropylene oxide, poly- or oligoethoxylêt alkylphenols are used.
  • ionic emulsifiers which can be used are alkyl, aryl and alkylaryl sulfonates, sulfates, phosphonates, phosphates or substances having other anionic or cationic end groups. It is also possible to introduce oligo- or polyalkylene oxide units between the ionic polar head group and the nonpolar unit of the emulsifier.
  • Typical ionic emulsifiers which can be used in dispersions according to the invention are, for example, sodium lauryl sulfate, sodium lauryl di- and triglycol ether sulfate, sodium undecyl heptaglycol ether sulfate, tri (sec-butyl) phenyl heptaglycol ether sulfate, sodium dodecylbenzenesulfonate and preferably the alkali metal or ammonium salts of fatty alcohol polyglycol ether sulfosuccinates such as Aerosol® A 102 from Cytec or Disponil® SUS 87 Spezial IS from Cognis.
  • water-soluble copolymers D) are preferably styrene-maleic anhydride copolymers having a molecular weight of 1000 to 4000 g / mol, which are wholly or partially neutralized with ammonium hydroxide or alkali metal hydroxides, added subsequently.
  • modified styrene-maleic anhydride copolymers (SMA® resins) and their partial esters can be used.
  • SMA® resins should not contain amino groups reactive with the cyclohexylepoxysilanes.
  • the modification of the SMA® resin can also be done in situ.
  • copolymers A) are accessible by the methods of radical substance, solution, suspension and emulsion polymerization known to the person skilled in the art, the emulsion polymerization being the preferred preparation process.
  • the copolymer A) is accordingly preferably prepared by emulsion polymerization of the monomers a) and b) and optionally c) to f) in an aqueous medium in the presence of free-radical initiators and emulsifiers and optionally protective colloids, molecular weight regulators and / or other auxiliaries.
  • Particularly suitable protective colloids in the emulsion polymerization are low molecular weight carboxymethylcelluloses, such as the commercially available products Blanose® 7M, Blanose® 7UL and Blanose® TEL from Clariant GmbH, and Ambergum® 3021 from Hercules.
  • carboxymethylcellulose is still modified with additional radicals as with hydroxyalkyl or alkyl groups. If required, it is also possible to use alkyloxyalkyl-modified carboxymethylcelluloses.
  • the polymerization is carried out by metering a monomer emulsion, but it can also be prepared by the batch, monomer feed or so-called power feed process. In the latter case, the monomers are metered in as such or in monomer emulsion with a gradient in the monomer composition.
  • the protective colloid (s) may be introduced in whole or in part in the reactor or else be metered in with the monomer emulsion or with the monomers.
  • Water and / or oil-soluble initiators are used to initiate the emulsion polymerization.
  • the emulsion polymerization can be initiated and maintained by thermal decomposition of the initiator or by redox polymerization. In the latter case, the reaction can be carried out even at temperatures below or at room temperature.
  • the emulsion polymerization is carried out at reactor temperatures between 50 and 85 ° C.
  • Suitable initiators are e.g. Hydrogen peroxide, potassium, sodium or ammonium peroxodisulfate, t-butyl hydroperoxide, lauryl hydroperoxide, dibenzoyl peroxide and other organoperoxides.
  • the polymerization can also be carried out in the presence of one or more reducing substances such as sodium metabisulfite, Rongalit®, ascorbic acid, glucose (redox polymerization).
  • catalytically active metal salts such as iron (III) chloride are preferably added to accelerate the formation of radicals.
  • regulators such as mercaptans, in particular n-dodecyl mercaptan, thiophenol or alcohols.
  • Usual additional amounts of the regulator are between 0.05 and 0.3% by weight, based on the total weight of the copolymer.
  • the dispersions of the invention are adjusted to a pH of 3 to 10 with one or more bases.
  • the pH adjustment can also be carried out by neutralization of the monomer emulsion and / or base with bases prior to the polymerization.
  • the pH of the monomer feed may be adjusted by dosing the (partially) neutralized (meth) acrylic acid present in aqueous solution or suspension.
  • oxirane and alkoxysilane groups present in the emulsion polymer dispersion are more stable to hydrolysis at a pH range between 4 and 7 than in an acidic or alkaline medium.
  • Ammonium, alkali metal and / or alkaline earth metal hydroxide and sodium carbonate solutions are preferably used as bases for pH adjustment. Alternatively, other buffer solutions or bases may be used.
  • coalescing agents such as white spirit, Texanol, butyldiglycol, plasticizers, such as dimethyl phthalate and dibutyl phthalate, thickeners based on polyacrylates and / or polyurethanes may also be added to the novel copolymer dispersions. Examples of suitable thickeners are Borchigel® L 75 N from Borchers, Tafigel® PUR 40 from Münzing-Chemie, DSX® 1550 from Cognis.
  • Preservatives Preservatives, defoamers, wetting agents, UV stabilizers, anticorrosion inhibitors and pigments, inorganic silica colloid dispersions, fillers, pigments and other additives known to those skilled in the art for preparing coating compositions may also be added.
  • novel aqueous copolymer dispersions are particularly suitable for use in elastic facade paints and roof coatings, sealants and sealing slurries, binders for leather fibers and in adhesives.
  • the preparations are characterized by very good restoring force after stretching of the coatings.
  • Films of the coatings to be tested were coated on a polyethylene film with a 400 ⁇ m doctor blade and kept at 23 ° C. and 50% relative humidity for 7 days stored. Then 6 test specimens per coating with the dimensions 110 mm * 15 mm were triggered with a punch and the thickness of the coating test specimens was determined with a Deltascope coating thickness meter from Fischer and noted. The films were then clamped in a Instron type 4302 tensile testing machine with 100N load cell and commercial PC control. Here, the free film length between the jaws was 60 mm. Then it was stretched at a pulling speed of 200mm / min until the film broke.
  • the PC program detects the (tear) elongation and the tensile stress up to the film break, furthermore the Young's module as well as the breakage energy absorption. To determine these data, the dry film thickness must be entered in the PC program before the test.
  • the particle size of the polymer dispersions was determined by means of photon correlation spectroscopy at a scattering angle of 90 ° as the weight average (d w ).
  • the copolymer dispersion used was a UV-crosslinking acrylate dispersion for elastomeric coatings containing about 55% by weight of Mowilith® LDM 7900 from Celanese Emulsions GmbH.
  • the coatings 4b and 4d which are based on the cyclohexylepoxisilan copolymers according to the invention, characterized by an increased tensile stress and thus increased restoring force after the elongation of the coating.

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Abstract

An aqueous copolymer dispersion (I) is prepared by radical polymerization of: (a) at least one ester of a 3-6C alpha ,beta -monoethylenically unsaturated carboxylic acid and 1-18C alcohols and optionally a vinyl aromatic compound and; (b) a mono- or multibasic alpha ,beta -monoethylenically unsaturated acid and/or corresponding anhydride with subsequent addition of at least one cycloalkyl epoxysilane to the resulting copolymer emulsion. Independent claims are included for: (1) a process for the production of the dispersion (I) by radical polymerization of the monomers in an aqueous medium in the presence of water soluble radical initiators, emulsifiers and/or protective colloids, regulators and/or other additives by emulsion polymerization with subsequent addition of a cycloalkyl epoxysilane, preferably functionalized and of formula (1) at 25-90 [deg]C, optionally with a UV-initiator, emulsifiers and water soluble copolymers; (2) coating agents (II) containing the dispersion (I) and pigment, fillers, dispersing agents, wetting agents, UV-filters, flame retardants, thickening agents, plasticizers and defoaming agents. [Structure I, p12] (1) R1>-R3>1-10C alkoxy having oxygen bonding to the silicon atom and/or alkyl; R4>1-10C alkylene.

Description

Die vorliegende Erfindung betrifft wässrige Copolymerisatdispersionen, Verfahren zu ihrer Herstellung sowie ihre Verwendung in Beschichtungsmitteln.The present invention relates to aqueous copolymer dispersions, processes for their preparation and their use in coating compositions.

Zur Herstellung von Beschichtungen werden häufig Copolymerisate eingesetzt, die durch den Einsatz von funktionellen Monomeren vernetzt werden. Sollen elastische Beschichtungen oder Filme hergestellt werden so werden deren elastischen Eigenschaften durch ihre Dehnungs- und Elastizitätsmoduli charakterisiert. Die Dehnungs-Elastizitätsmoduli der Polymerisate können hierbei durch Variation der Vernetzermenge über einen weiten Bereich eingestellt werden.For the production of coatings copolymers are often used, which are crosslinked by the use of functional monomers. If elastic coatings or films are to be produced, their elastic properties are characterized by their expansion and elastic moduli. The elastic moduli of elasticity of the polymers can be adjusted by varying the amount of crosslinker over a wide range.

Es ist bekannt, Copolymerisate durch Emulsionspolymerisation herzustellen. Als Vernetzer setzt man dabei entweder bi- oder oligo-olefinisch ungesättigte Monomere, wie zum Beispiel Hexandioldimethacrylat, oder funktionelle Monomere oder Metallkomplexe ein, die im allgemeinen erst bei der Filmbildung zur Vernetzung führen. Geeignete Metallkomplexe lassen sich von Übergangsmetallen der Gruppe 4A des Periodensystems, wie Zirkonium, ableiten (P.J. Moles, Polym. Paint Colour J. 1988, 178, Seite 154).It is known to prepare copolymers by emulsion polymerization. Suitable crosslinkers are either bi- or oligo-olefinically unsaturated monomers, such as, for example, hexanediol dimethacrylate, or functional monomers or metal complexes, which generally lead to crosslinking only during film formation. Suitable metal complexes can be derived from group 4A transition metals of the periodic table, such as zirconium (P.J. Moles, Polym., Paint Color J. 1988, 178, page 154).

Vernetzer, die mehrere ethylenisch-ungesättigte Gruppen aufweisen, führen zu einer mehr oder minder homogenen Vernetzung innerhalb der Dispersionspartikel, während benachbarte Partikel nur durch Verschlaufung von Polymerkettenenden physikalisch vernetzt werden.Crosslinkers which have several ethylenically unsaturated groups lead to a more or less homogeneous crosslinking within the dispersion particles, while adjacent particles are physically crosslinked only by entanglement of polymer chain ends.

Darüber hinaus sind auch Reaktivvernetzungssysteme bekannt, bei denen es neben einer Vernetzung der Polymerketten in den Polymerpartikeln auch zu einer interpartikulären Vernetzungsreaktion benachbarter Polymerpartikel bei der Filmbildung kommt. Typische Reaktivvernetzermonomere, die als funktionelle Einheiten im Copolymerisat eingebaut werden, sind N-Methylolacrylamid (NMAA) oder olefinisch ungesättigte Silane und Epoxide, wie Vinyltrimethoxysilan oder Glycidylmethacrylat.
Wässrige Copolymerisatdispersionen, in denen monoethylenisch ungesättigte, vernetzende Silane einpolymerisiert werden, sind aus DE 198 58 851 A1 bekannt. Als bevorzugte Silane werden Vinyltrimethoxysilan oder Silane enthaltend Epoxid-Gruppen, wie die Glycidyl-Gruppe, verwendet. Beschichtungen und Filme auf Basis derartiger Copolymerisatdispersionen weisen eine erhöhte Elastizität auf.
Aus Database Chemabs., XP002292939 sind Silankoppler für wässrige Beschichtungsmittel bekannt.
EP 0 640 929 A1 (=DE 43 29 089 A) beschreibt ein Verfahren zur Herstellung von wässrigen silanolgruppenmodifizierten Kunststoffdispersionen durch polymeranaloge Umsetzung mit Epoxisilanen.
Aus DE 43 29 089 A1 ist bekannt, während der Polymerisationsreaktion Epoxisilane, beispielsweise Glycidyloxypropyltrimethoxysilan zuzusetzen. Derartige Dispersionen werden vor allem im Bautenschutzbereich eingesetzt und zeichnen sich durch eine sehr gute Nasshaftzugfestigkeit bei der Verwendung in Fliesenklebern sowie durch ein sehr gutes Pigmentbindevermögen in Farben aus.In addition, reactive crosslinking systems are known in which, in addition to crosslinking of the polymer chains in the polymer particles, also to a interparticle crosslinking reaction of adjacent polymer particles in the film formation comes. Typical reactive crosslinker monomers which are incorporated as functional units in the copolymer are N-methylolacrylamide (NMAA) or olefinically unsaturated silanes and epoxides, such as vinyltrimethoxysilane or glycidyl methacrylate.
Aqueous copolymer dispersions in which monoethylenically unsaturated, crosslinking silanes are copolymerized are known from DE 198 58 851 A1. Preferred silanes are vinyltrimethoxysilane or silanes containing epoxide groups, such as the glycidyl group. Coatings and films based on such copolymer dispersions have an increased elasticity.
Database Chemabs., XP002292939 discloses silane couplers for aqueous coating compositions.
EP 0 640 929 A1 (= DE 43 29 089 A) describes a process for the preparation of aqueous silanol-group-modified polymer dispersions by polymer-analogous reaction with epoxysilanes.
From DE 43 29 089 A1 it is known to add epoxysilanes, for example glycidyloxypropyltrimethoxysilane, during the polymerization reaction. Such dispersions are mainly used in the building protection sector and are characterized by a very good wet-tensile strength when used in tile adhesives and by a very good pigment binding capacity in colors.

Auch die nachträgliche Zugabe von Epoxisilanen zur Modifizierung des bereits gebildeten Copolymerisats ist bekannt. So behandelt EP 0 214 696 A1 die nachträgliche Zugabe von 3-Glycidoxypropyltrimethoxysilan zu einem Styrol/Butylacrylat/Acrylsäure-Copolymerisat. Die nachträgliche Modifizierung mit Epoxysilanen erhöht die Nasszugspannung solcher auf einem hohen Styrolanteil basierenden Klebern auf keramischem Material.
US-A-4,077,932 und US-A-4,032,487 befassen sich mit wässrigen Klebstoffzusammensetzungen, die auf Copolymerisaten basieren, in denen Stickstoff haltige Monomere, wie zum Beispiel Dimethylaminomethylmethacrylat, einpolymerisiert werden. Die Modifizierung durch nachträgliche Zugabe von Epoxisilanen, wie zum Beispiel von Glycidoxypropyltrimethoxysilan, erhöht die Widerstandsfähigkeit gegenüber Feuchtigkeit und erhöht die Zugspannung der Filme. Durch die Anwesenheit von reaktiven Aminogruppen in dem Copolymerisat kommt es jedoch zu einer vorzeitigen Reaktion zwischen dem Polymer und dem Epoxisilan während der Lagerung der Klebstoffzusammensetzung.The subsequent addition of epoxy silanes for modifying the already formed copolymer is also known. Thus, EP 0 214 696 A1 deals with the subsequent addition of 3-glycidoxypropyltrimethoxysilane to a styrene / butyl acrylate / acrylic acid copolymer. Subsequent modification with epoxysilanes increases the wet tensile stress of such high styrene-based adhesives on ceramic material.
US-A-4,077,932 and US-A-4,032,487 are concerned with aqueous adhesive compositions based on copolymers in which nitrogen-containing monomers, such as dimethylaminomethyl methacrylate, are copolymerized. Modification by subsequent addition of epoxysilanes, such as glycidoxypropyltrimethoxysilane, increases moisture resistance and increases tensile stress Movies. However, the presence of reactive amino groups in the copolymer causes a premature reaction between the polymer and the epoxysilane during storage of the adhesive composition.

Lagerstabile Dispersionen lassen sich nach US-A-6,127,462 dadurch erhalten, indem man carboxylgruppenhaltige Polymerisate mit Epoxisilanen, beispielsweise 2-(3,4-Epoxycyclohexyl)ethyltriethoxysilan, modifiziert und vor der Anwendung als Beschichtungsmittel durch Katalysatorzugabe die Vernetzungsreaktion mit dem Epoxisilanvernetzer einleitet. Als Katalysatoren werden tertiäre Amine oder zinnorganische Verbindungen empfohlen. Die bekannten Zusammensetzungen weisen selbst nach der Lagerung noch eine hohe Klebefähigkeit aus. Die bekannten Zusammensetzungen erfordern jedoch die Anwesenheit von Katalysatoren, beispielsweise von tertiären Aminen, die in Gegenwart von Sauerstoff bei längerer Lagerung zu unerwünschten und gefärbten Zersetzungsprodukten führen können. Wird das katalytische Material schon bei der Herstellung der Zubereitung zugesetzt, so verringert sich ihre Lagerstabilität.According to US Pat. No. 6,127,462, storage-stable dispersions can be obtained by modifying carboxyl-containing polymers with epoxysilanes, for example 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and initiating the crosslinking reaction with the epoxysilane crosslinker prior to use as a coating agent by addition of a catalyst. As catalysts, tertiary amines or organotin compounds are recommended. The known compositions still have a high adhesive capacity even after storage. The known compositions, however, require the presence of catalysts, for example tertiary amines, which in the presence of oxygen may, on prolonged storage, lead to undesired and colored decomposition products. If the catalytic material is added already during preparation of the preparation, its storage stability is reduced.

Es wurde nun überraschenderweise gefunden, dass sich in Beschichtungen, insbesondere in elastischen Beschichtungen die Reißdehnung, die Zugspannung beim Bruch und die Filmkohäsionsenergie gleichzeitig erhöhen lassen, wenn man wässrigen Copolymerisatdispersionen geringe Mengen an Cycloalkylepoxisilanen zusetzt.It has now surprisingly been found that in coatings, in particular in elastic coatings, the elongation at break, the tensile stress at break and the film cohesion energy can be simultaneously increased if small amounts of cycloalkylepoxysilanes are added to aqueous copolymer dispersions.

Bei der Verwendung von Vernetzersystemen in Copolymerisatdispersionen beobachtet man im allgemeinen eine gegenläufige Kopplung von Reißdehnung und Zugspannung, das heißt, dass mit zunehmender Reißdehnung die Zugspannung sich verkleinert. Es gibt nur wenige Beispiele für Vernetzersysteme, bei denen die übliche antagonistische Kopplung von Reißdehnung und Zugspannung aufgehoben ist, also bei erhöhter Vernetzerkonzentration im Copolymerisat eine erhöhte Zugspannung bei gleichbleibender oder erhöhter Reißdehnung zu beobachten ist.When crosslinking systems are used in copolymer dispersions, an opposite coupling of elongation at break and tensile stress is generally observed, that is, the tensile stress decreases as the elongation at break increases. There are only a few examples of crosslinker systems in which the usual antagonistic coupling of elongation at break and tensile stress is eliminated, so at elevated crosslinker concentration in the copolymer an increased tensile stress at constant or increased elongation at break is observed.

Aus Surface Coatings Australia 1995, 32 (5), Seite 18 ist die Vernetzung von Dispersionspolymerisaten durch mehrwertige Metallionen bekannt. Die Zugspannung der Filme nimmt bei in etwa gleichbleibender Reißdehnung der Polymerisate durch die Vernetzung synergetisch zu.From Surface Coatings Australia 1995, 32 (5), page 18, the crosslinking of dispersion polymers by polyvalent metal ions is known. The Tensile stress of the films increases synergistically at about the same elongation at break of the polymers due to crosslinking.

Proc. Int. Conf. Org. Coat.: Waterborne, High Solids, Powder Coat., 24th (1998), 503-521 beschreibt heterogene Polymerisate, die durch Schwellen eines weichen Emulsionspolymerisats mit einer zweiten Monomerdosierung und anschließende Fortsetzung der Polymerisation erzeugt werden. Die zweite Monomerdosierung führt zur Ausbildung kleiner, harter Domänen umgeben von weicher Matrix in den Polymerisatteilchen, die nach der Filmbildung durch Transmissionselektronenmikroskopie visualisiert werden können. Die entsprechenden Polymerfilme weisen gesteigerte Reißdehnungs- und Zugspannungswerte auf.Proc. Int. Conf. Org. Coat .: Waterborne, High Solids, Powder Coat., 24 th (1998), 503-521 describes heterogeneous polymers which are produced by swelling of a soft emulsion polymer with a second monomer feed and subsequent continuation of the polymerization. The second monomer dosage results in the formation of small, hard domains surrounded by soft matrix in the polymerizate particles, which can be visualized after film formation by transmission electron microscopy. The corresponding polymer films have increased elongation at break and tensile values.

Die vorliegende Erfindung betrifft wässrige Copolymerisatdispersion erhältlich durch radikalische Polymerisation zumindest der Monomeren a) und b) und durch nachträgliche Zugabe von mindestens einem Cycloalkylepoxysilan zu der erhaltenen Copolymerisatemulsion, wobei Monomer a) ein Ester aus 3 bis 6 C-Atome enthaltenden α,β-monoethylenisch ungesättigten Carbonsäuren sowie 1 bis 18 C-Atome enthaltenden Alkanolen und gegebenenfalls eine vinylaromatische Verbindung ist oder ein Gemisch dieser Monomeren bedeutet und wobei Monomer b) eine ein- oder mehrbasische α,β-monoethylenisch ungesättigte Säure und/oder deren Anhydrid bedeutet.The present invention relates to aqueous copolymer dispersion obtainable by free-radical polymerization of at least the monomers a) and b) and by subsequent addition of at least one cycloalkylepoxysilane to the resulting copolymer emulsion, wherein monomer a) is an ester of α, β-monoethylenic containing 3 to 6 C atoms unsaturated carboxylic acids and alkanols containing 1 to 18 C atoms and optionally a vinylaromatic compound or a mixture of these monomers and wherein monomer b) is a mono- or polybasic α, β-monoethylenically unsaturated acid and / or their anhydride.

Bevorzugt werden wässrige Copolymerisatdispersion, die zusätzlich zu den Monomeren a) und b) sich noch mindestens von einem der Monomeren c), d), e) und/oder f) ableiten, wobei Monomer c) ein di-oder oligoethylenisch ungesättigtes vernetzendes Monomer oder ein Gemisch dieser Monomeren bedeutet, Monomer d) ein 3 bis 8 C-Atome enthaltendes α,β-monoethylenisch ungesättigtes Carbonsäureamid oder ein Gemisch dieser Monomeren bedeutet, Monomer e) ein Reaktivvernetzermonomer, ausgewählt aus einer Kombination mindestens eines ethylenisch ungesättigten Silans mit mindestens einem ethylenisch ungesättigten Monomeren mit einer Oxirangruppe oder einem Gemisch dieser Monomeren bedeutet und Monomer f) ein sonstiges copolymerisierbares ethylenisch ungesättigtes Monomer oder ein Gemisch dieser Monomeren, ausgenommen ein stickstoffhaltiges, mit Epoxygruppen reagierendes Monomer, bedeutet.Preference is given to aqueous copolymer dispersion which, in addition to the monomers a) and b), is also derived from at least one of the monomers c), d), e) and / or f), wherein monomer c) is a di- or oligoethylenically unsaturated crosslinking monomer or a mixture of these monomers, monomer d) is an α, β-monoethylenically unsaturated carboxylic acid containing 3 to 8 C atoms or a mixture of these monomers, monomer e) is a reactive crosslinker monomer selected from a combination of at least one ethylenically unsaturated silane with at least one ethylenic unsaturated monomer having an oxirane group or a mixture of these monomers and monomer f) is another copolymerizable ethylenic unsaturated monomer or a mixture of these monomers except a nitrogen-containing epoxy group-reactive monomer.

In einer weiteren bevorzugten Ausführungsform betrifft die Erfindung die oben definierten wässrigen Copolymerisatdispersion mit einem Feststoffanteil von 20 - 65 Gew. %, wobei das Copolymerisat sich ableitet von 40 bis 99,8 Gew. % an Monomer a) oder deren Gemischen, von 0,1 bis 10 Gew. % an Monomer b) oder deren Gemischen, von 0 bis 10 Gew. % an Monomer c) oder deren Gemischen, von 0 bis 5 Gew. % an Monomer d) oder deren Gemischen, von 0 bis 5 Gew. % an Monomer e) oder deren Gemischen, und von 0 bis 30 Gew. % an Monomer f) oder deren Gemischen, wobei die Mengenangaben an Monomer auf die Gesamtmenge an eingesetztem Monomer bezogen sind.In a further preferred embodiment, the invention relates to the above-defined aqueous copolymer dispersion having a solids content of 20-65% by weight, the copolymer being derived from 40 to 99.8% by weight of monomer a) or mixtures thereof, of 0.1 to 10% by weight of monomer b) or mixtures thereof, from 0 to 10% by weight of monomer c) or mixtures thereof, from 0 to 5% by weight of monomer d) or mixtures thereof, from 0 to 5% by weight to monomer e) or mixtures thereof, and from 0 to 30% by weight of monomer f) or mixtures thereof, the amounts of monomer being based on the total amount of monomer used.

Eine weitere bevorzugte Ausführungsform der vorliegenden Erfindung betrifft die oben definierten wässrigen Copolymerisatdispersionen, wobei die Gewichtsanteile der Monomeren a) und b) so gewählt werden, dass ein nur aus diesen Monomeren aufgebautes Copolymerisat eine Glasübergangstemperatur im Bereich zwischen -50 bis 120°C, vorzugsweise zwischen -50 und 15 °C aufweisen würde.A further preferred embodiment of the present invention relates to the above-defined aqueous copolymer dispersions, wherein the weight proportions of the monomers a) and b) are chosen so that a copolymer composed only of these monomers has a glass transition temperature in the range from -50 to 120 ° C, preferably between -50 and 15 ° C would have.

Bei dem erfindungsgemäß eingesetzten Cycloalkylepoxisilan handelt es sich bevorzugt um eine Verbindung der allgemeinen Formel (I)

Figure imgb0001
wobei R1, R2 und R3 lineare oder verzweigte Alkoxyreste mit Bindung des Sauerstoffatoms zum Siliciumatom und/oder Alkylreste mit 1-10 CAtomen bedeuten und R4 ein linearer oder verzweigter Alkylenrest mit 1-10 C-Atomen darstellt.The cycloalkylpoxysilane used according to the invention is preferably a compound of the general formula (I)
Figure imgb0001
 where R 1 , R 2 and R 3 are linear or branched alkoxy radicals with bonding of the oxygen atom to the silicon atom and / or alkyl radicals having 1-10 C atoms and R 4 is a linear or branched alkylene radical having 1-10 C atoms.

Die erfindungsgemäßen wässrigen Copolymerisatdispersionen enthalten vorzugsweise ein oder mehrere UV-Initiatoren B) und/oder ein oder mehrere Emulgatoren C), und/oder ein oder mehrere wasserlösliche Copolymerisate D).The novel aqueous copolymer dispersions preferably contain one or more UV initiators B) and / or one or more emulsifiers C), and / or one or more water-soluble copolymers D).

In einer weiteren bevorzugten Ausführungsform betrifft die Erfindung wässrige Copolymerisatdispersionen mit einem Feststoffanteil von 20 - 65 Gew.-%, dadurch erhältlich, dass
ein Copolymerisat A) im wesentlichen bestehend aus

  • a) 40 bis 99,8 Gew. %, vorzugsweise 65 bis 85 Gew. % mindestens eines Esters aus 3 bis 6 C-Atome enthaltenden a, β-monoethylenisch ungesättigten Carbonsäuren sowie 1 bis 18 C-Atome enthaltenden Alkanolen und 0 bis 30 Gew. % mindestens einer vinylaromatischen Verbindung (Monomere a),
  • b) 0,1 bis 10 Gew. % mindestens einer ein- oder mehrbasischen (a, βmonoethylenisch ungesättigten Säure oder deren Anhydriden (Monomere b),
  • c) 0 bis 10 Gew. %, bevorzugt 0 - 0,5 Gew. % mindestens eines di- oder oligoethylenisch ungesättigten vernetzenden Monomeren (Monomere c),
  • d) 0 bis 5 Gew.-% wenigstens eines 3 bis 8 C-Atome enthaltenden (a, β-monoethylenisch ungesättigten Carbonsäureamids, welches am Stickstoff einfach oder doppelt mit bis zu 5 C-Atomen enthaltenden Alkylengruppen, Alkylsulfaten, Alkylsulfonaten, Alkylphosphaten, Alkylethern oder Alkylethersulfaten oder -phosphaten substituiert sein kann (Monomere d),
  • e) 0 bis 5 Gew. %, bevorzugt 0 bis 2 Gew.-% Reaktivvernetzermonomere, ausgewählt aus einer Kombination mindestens eines ethylenisch ungesättigten Silans mit mindestens einem ethylenisch ungesättigten Monomeren mit einer Oxirangruppe (Monomere e),
  • f) 0 bis 30 Gew.-% mindestens eines sonstigen copolymerisierbaren ethylenisch ungesättigten Monomeren (Monomere f), ausgenommen stickstoffhaltige, mit Epoxygruppen reagierende Monomere,
wobei sich die Gewichtsanteile auf das Gesamtgewicht an Monomeren beziehen und die Gewichtsanteile der Monomeren a) und b) innerhalb der beschriebenen Grenzen so gewählt werden, dass ein nur aus diesen Monomeren aufgebautes Copolymerisat eine Glasübergangstemperatur im Bereich zwischen -50 und 15 °C aufweisen würde;
durch Polymerisation der Monomeren a) bis f) in Wasser hergestellt wird und zu der so erhaltenen wässrigen Copolymerisatdispersion nachträglich ein oder mehrere funktionelle Cyclohexylepoxysilane der allgemeinen Formel (I)
Figure imgb0002
 wobei R1, R2 und R3 lineare oder verzweigte Alkoxyreste mit Bindung des Sauerstoffatoms zum Siliciumatom und/oder Alkylreste mit 1-10 C-Atomen bedeuten und R4 ein linearer oder verzweigter Alkylenrest mit 1-10 C-Atomen darstellt, bei Temperaturen zwischen 25 und 90°C zugegeben werden;
und gegebenenfalls ein oder mehrere UV-Initiatoren B) in einer Menge von 0 bis 5 Gew. %, bevorzugt 0,05 bis 0,5 Gew. %, bezogen auf das Copolymerisat A);
gegebenenfalls ein oder mehrere Emulgatoren C) in einer Menge von 0 bis 10 Gew. %, bezogen auf das Copolymerisat A); und
gegebenenfalls ein oder mehrere wasserlösliche Copolymerisate D) in einer Menge von 0 bis 4 Gew. %, bezogen auf das Copolymerisat A), nachträglich zu der wässrigen Copolymerisatdispersion zugegeben werden.In a further preferred embodiment, the invention relates to aqueous copolymer dispersions having a solids content of 20-65 wt .-%, obtainable by, that
a copolymer A) consisting essentially of
  • a) 40 to 99.8 wt.%, Preferably 65 to 85 wt.% Of at least one ester of 3 to 6 carbon atoms containing α, β-monoethylenically unsaturated carboxylic acids and 1 to 18 carbon atoms containing alkanols and 0 to 30 wt % of at least one vinyl aromatic compound (monomers a),
  • b) 0.1 to 10% by weight of at least one mono- or polybasic (α, β-monoethylenically unsaturated acid or its anhydrides (monomers b),
  • c) 0 to 10% by weight, preferably 0 to 0.5% by weight of at least one di- or oligoethylenically unsaturated crosslinking monomer (monomers c),
  • d) 0 to 5 wt .-% of at least one 3 to 8 carbon atoms-containing (α, β-monoethylenically unsaturated carboxylic acid which on the nitrogen single or double with up to 5 carbon atoms containing alkylene groups, alkyl sulfates, alkyl sulfonates, alkyl phosphates, alkyl ethers or alkyl ether sulfates or phosphates may be substituted (monomers d),
  • e) 0 to 5% by weight, preferably 0 to 2% by weight, of reactive crosslinker monomers selected from a combination of at least one ethylenically unsaturated silane with at least one ethylenically unsaturated monomer having an oxirane group (monomers e),
  • f) 0 to 30% by weight of at least one other copolymerizable ethylenically unsaturated monomer (monomers f), with the exception of nitrogen-containing monomers which react with epoxy groups,
wherein the proportions by weight relate to the total weight of monomers and the proportions by weight of the monomers a) and b) within the limits described are chosen so that one composed only of these monomers Copolymer would have a glass transition temperature in the range between -50 and 15 ° C;
by polymerization of the monomers a) to f) in water, and to the aqueous copolymer dispersion thus obtained subsequently one or more functional cyclohexylepoxysilanes of the general formula (I)
Figure imgb0002
 where R 1 , R 2 and R 3 are linear or branched alkoxy radicals with bonding of the oxygen atom to the silicon atom and / or alkyl radicals having 1-10 C atoms and R 4 is a linear or branched alkylene radical having 1-10 C atoms, at temperatures be added between 25 and 90 ° C;
and optionally one or more UV initiators B) in an amount of 0 to 5% by weight, preferably 0.05 to 0.5% by weight, based on the copolymer A);
optionally one or more emulsifiers C) in an amount of 0 to 10% by weight, based on the copolymer A); and
optionally one or more water-soluble copolymers D) in an amount of 0 to 4 wt.%, Based on the copolymer A), be added subsequently to the aqueous copolymer dispersion.

Es wurde überraschenderweise gefunden, dass bereits bei sehr geringen Zusatzmengen von Cycloalkylepoxysilanen, vorzugsweise Cyclohexylepoxysilanen der allgemeinen Formel (I), zu wässrigen Copolymerisatdispersionen eine stark erhöhte Bruchenergie in Beschichtungen beobachtet wird. Dieses trifft insbesondere zu für elastische Beschichtungen mit tiefer Glastemperatur des Copolymers A) von-50 bis +15°C. Die Menge an zugesetztem Cycloalkylepoxysilan ist nur sehr klein und beträgt typischerweise bis zu 1 Gew. %, bezogen auf die wässrige Dispersion des Copolymerisats A).It has surprisingly been found that even with very small addition amounts of cycloalkylepoxysilanes, preferably cyclohexylepoxysilanes of the general formula (I), a greatly increased fracture energy in coatings is observed in aqueous copolymer dispersions. This is especially true for elastic coatings with low glass transition temperature of the copolymer A) from -50 to + 15 ° C. The amount of cycloalkylepoxysilane added is only very small and is typically up to 1% by weight, based on the aqueous dispersion of the copolymer A).

Vorzugsweise werden Mengen an Cycloalkylepoxysilanen von bis zu 0,5 Gew. %, insbesondere von bis zu 0,25 Gew. %, bezogen auf die wässrige Dispersion des Copolymerisats A), zugesetzt.Preferably amounts of cycloalkylepoxysilanes of up to 0.5% by weight, in particular of up to 0.25% by weight, based on the aqueous dispersion of the copolymer A), are added.

Die Mindestmenge an den Cycloalkylepoxysilanen beträgt 0,05 Gew.-%, bezogen auf die wässrige Dispersion des Copolymerisats A).The minimum amount of the Cycloalkylepoxysilanen is 0.05 wt .-%, based on the aqueous dispersion of the copolymer A).

Vorzugsweise bedeuten in der allgemeinen Formel (I) R1, R2 und R3 jeweils unabhängig voneinander -OCH3 oder -OC2H5 und R4 -C2H4-.Preferably, in the general formula (I), R 1 , R 2 and R 3 each independently represent -OCH 3 or -OC 2 H 5 and R 4 -C 2 H 4 -.

Als Ester von 3 bis 6 C-Atome enthaltenden α,β-monoethylenisch ungesättigten Carbonsäuren und 1 bis 18 C-Atome enthaltenden Alkanolen werden Ester der Acryl- und/oder Methacrylsäure vorzugsweise eingesetzt.As esters of α, β-monoethylenically unsaturated carboxylic acids containing 3 to 6 carbon atoms and alkanols containing 1 to 18 carbon atoms, esters of acrylic and / or methacrylic acid are preferably used.

Weitere bevorzugte Ausführungsformen werden in den Ansprüche 12-18 sowie in den Ansprüchen 19-20, 21-25 und 26 beansprucht.Further preferred embodiments are claimed in claims 12-18 and in claims 19-20, 21-25 and 26.

Es wurden bei diesen geringen Zusatzmengen überraschenderweise Steigerungen der Bruchenergien um bis zu 84% bezogen auf den Ausgangswert ermittelt. Die Beschichtungen weisen hierbei keine reduzierten Reißdehnungswerte auf.Surprisingly, increases in fracture energies of up to 84% based on the initial value were determined with these small additional amounts. The coatings have no reduced elongation at break.

Die synergetische Erhöhung der Zugspannung und Reißdehnung bedeutet eine Verbesserung der anwendungstechnischen Eigenschaften der mit den erfindungsgemäßen Copolymerisatdispersionen hergestellten Beschichtungen. Die hieraus resultierende Erhöhung des zum Filmriss notwendigen Energieeintrags bewirkt eine erhöhte Rissüberbrückung bei gegebener einwirkender Energie, wie sie beispielsweise bei einer Rissaufweitung einer gestrichenen Hausfassade auftritt. Eine wesentliche Absenkung der Reißdehnung zu Gunsten erhöhter Zugspannung wirkt sich hier nachteilig aus, da die Reißdehnung im allgemeinen direkt proportional zum Rissüberbrückungsvermögen ist. Die Kohäsionsenergie von Polymerfilmen ist proportional zur Fläche unter der Zugspannungs-/Reißdehnungskurve und kann in Reißdehnungsversuchen experimentell ermittelt werden.The synergetic increase in the tensile stress and elongation at break mean an improvement in the performance properties of the coatings produced with the novel copolymer dispersions. The resulting increase in the energy required for the film tear causes increased crack bridging at a given acting energy, as occurs, for example, in a crack expansion of a painted house facade. A substantial reduction of the elongation at break in favor of increased tensile stress has a disadvantageous effect here, since the elongation at break is generally directly proportional to the crack bridging capacity. The cohesive energy of polymer films is proportional to the area under the tensile / ultimate elongation curve and can be determined experimentally in tensile elongation tests.

Die Cycloalkylepoxysilane werden der wässrigen Copolymerisatdispersion A) zugesetzt. Ihre Zugabe erfolgt also nach der eigentlichen Copolymerisation der Monomere a) und b), gegebenenfalls mit den Monomeren c) bis f), zu dem Copolymerisat A). Da nur kleine Mengen an Cycloalkylepoxysilanen als Nachgaben ausreichen, lassen sich die erfindungsgemäßen wässrigen Copolymerisatdispersionen sehr kostengünstig herstellen.The cycloalkylepoxysilanes are added to the aqueous copolymer dispersion A). Their addition is thus carried out after the actual copolymerization of Monomers a) and b), optionally with the monomers c) to f), to the copolymer A). Since only small amounts of Cycloalkylepoxysilanen sufficient as Nachgeben, the novel aqueous copolymer dispersions can be produced very inexpensively.

In einer bevorzugten Ausführungsform werden in der erfindungsgemäßen wässrigen Copolymerisatdispersion solche Copolymerisate eingesetzt, die eine niedrige Glasübergangstemperatur in einem Bereich von -50 bis +15°C aufweisen, wodurch auf den Einsatz von Härtungskatalysatoren für die Cycloalkylepoxysilane verzichtet werden kann.In a preferred embodiment, copolymers which have a low glass transition temperature in the range from -50 to + 15 ° C. are used in the aqueous copolymer dispersion according to the invention, which makes it possible to dispense with the use of curing catalysts for the cycloalkylepoxysilanes.

Gegebenenfalls können auch noch UV-Initiatoren B), Emulgatoren C) und wasserlösliche Copolymerisate D) als Nachgabe zu der wässrigen Copolymerisatdispersion hinzugefügt werden.Optionally, it is also possible to add UV initiators B), emulsifiers C) and water-soluble copolymers D) as a follow-up to the aqueous copolymer dispersion.

Die Bestimmung der Glasübergangstemperaturen der Copolymerisate erfolgt mittels DSC (Differential Scanning Calorimetry, 20°C/min, midpoint), die Monomerzusammensetzungen der durch die Glasübergangstemperatur charakterisierten Copolymerisate wird durch die Fox-Gleichung (T.G. Fox, Bull. Am. Phys. Soc. (Ser. II) 1956, 1, 123) unter Berücksichtigung der mittels DSC bestimmten Glasübergangstemperaturen der einzelnen Monomer-Homopolymerisate (wie zum Beispiel aus Emulsion Polymerization and Emulsion Polymers, John Wiley, Chichester 1997, Seite 624 bekannt) ermittelt.The glass transition temperatures of the copolymers are determined by means of DSC (Differential Scanning Calorimetry, 20 ° C./min, midpoint), the monomer compositions of the copolymers characterized by the glass transition temperature are determined by the Fox equation (TG Fox, Bull. Am. Phys. Soc. Ser. II) 1956, 1, 123), taking into account the glass transition temperatures, determined by means of DSC, of the individual monomer homopolymers (as known, for example, from Emulsion Polymerization and Emulsion Polymers, John Wiley, Chichester 1997, page 624).

Ebenfalls zeigen auch Copolymerisate, die ein Reaktivvernetzersystem aus mindestens einem ethylenisch ungesättigten Silan, beispielsweise Vinyltriethoxysilan, und mindestens einem ethylenisch ungesättigten Oxiranderivat, beispielsweise Glycidylmethacrylat, enthalten (Monomere e), die erfindungsgemäße synergetische Korrelation zwischen Zugspannung und Reißdehnung in Beschichtungen, nachdem sie mit den Cycloalkylepoxysilanen konfektioniert wurden.Likewise, copolymers which contain a reactive crosslinker system comprising at least one ethylenically unsaturated silane, for example vinyltriethoxysilane, and at least one ethylenically unsaturated oxirane derivative, for example glycidyl methacrylate (monomers e), also exhibit the synergistic correlation between tensile stress and elongation at break in coatings according to the invention after having reacted with the cycloalkylepoxysilanes were made up.

Das Copolymerisat A) ist aus den Monomeren a) und b) aufgebaut und gegebenenfalls können die Monomere c) bis f) jeweils einpolymerisiert werden.The copolymer A) is composed of the monomers a) and b) and, if appropriate, the monomers c) to f) can each be polymerized in copolymerized form.

Bei den Monomeren a) handelt es sich bevorzugt um Ester der (Meth)acrylsäure. Im folgenden bezeichnet (Meth)acrylsäure sowohl Acrylals auch Methacrylsäure und (Meth)acrylat Ester der Acryl- und Methacrylsäure.The monomers a) are preferably esters of (meth) acrylic acid. In the following, (meth) acrylic acid refers to both acrylic and methacrylic acid and (meth) acrylate esters of acrylic and methacrylic acid.

Bevorzugte vinylaromatische Verbindungen sind Styrol, Methylstyrol, Ethylstyrol, Dimethylstyrol, Diethylstyrol und Trimethylstyrol. Besonders bevorzugt ist hierbei Styrol.Preferred vinyl aromatic compounds are styrene, methylstyrene, ethylstyrene, dimethylstyrene, diethylstyrene and trimethylstyrene. Particularly preferred is styrene.

Als Monomere b) werden bevorzugt (Meth)acrylsäure, Itaconsäure, Fumar und Maleinsäure sowie deren Anhydride eingesetzt.As monomers b) it is preferred to use (meth) acrylic acid, itaconic acid, fumar and maleic acid and their anhydrides.

Auch die Halbamide und Halbester von ethylenisch ungesättigten Dicarbonsäuren eignen sich als Monomere b).The hemiamides and half esters of ethylenically unsaturated dicarboxylic acids are also suitable as monomers b).

Als vernetzende Monomere c) eignen sich besonders di- oder oligofunktionelle (Meth)acrylester, wie 1,6-Hexandioldi(meth)acrylat, 1,3- und 1,4-Butandioldi(meth)acrylat, Trimethylolpropantri(meth)acrylat. Bevorzugt werden Mengen zwischen 0 - 0,5 Gew. % an diesen Monomeren, bezogen auf das Gesamtgewicht der Monomeren.Suitable crosslinking monomers c) are especially di- or oligofunctional (meth) acrylic esters, such as 1,6-hexanediol di (meth) acrylate, 1,3- and 1,4-butanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate. Preference is given to amounts between 0 and 0.5% by weight of these monomers, based on the total weight of the monomers.

Geeignete Monomere d) sind besonders (Meth)acrylamid sowie 2-Acrylamido-2-methylpropansulfonsäure und ihre Salze.Suitable monomers d) are especially (meth) acrylamide and also 2-acrylamido-2-methylpropanesulfonic acid and its salts.

Als Monomere e) kommen ethylenisch ungesättigte Silane mit mindestens einem ethylenisch ungesättigten Rest in Kombination mit mindestens einem oxirangruppenhaltigen ethylenisch ungesättigten Monomer in Betracht. Eine solche Kombination bezeichnet man auch als Reaktiwernetzungssystem.Suitable monomers e) are ethylenically unsaturated silanes having at least one ethylenically unsaturated radical in combination with at least one oxirane group-containing ethylenically unsaturated monomer. Such a combination is also referred to as a reactivation system.

Besonders bevorzugt ist hierbei der Gebrauch von copolymerisierbaren Silanen der allgemeinen Formel CH2=CH-Si(OX)3, wobei X für Wasserstoff, eine Acylgruppe und/oder eine Alkylgruppe mit maximal 10 C-Atomen steht. Beispiele für solche Silane sind Vinyltrimethoxysilan und Vinyltriethoxysilan.Particularly preferred here is the use of copolymerizable silanes of the general formula CH 2 = CH-Si (OX) 3 , wherein X is hydrogen, an acyl group and / or an alkyl group having a maximum of 10 carbon atoms. Examples of such silanes are vinyltrimethoxysilane and vinyltriethoxysilane.

Weitere bevorzugte Silane sind solche der allgemeinen Formel CH2=CZ-COO-Y-Si(OX)3, wobei Z für Wasserstoff, eine Methyl- oder Ethylgruppe, Y für eine lineare oder verzweigte Alkylenkette mit 2 bis 6 C-Atomen und X für Wasserstoff, eine Acylgruppe und/oder eine Alkylgruppe mit maximal 10 C-Atomen steht. Ein Beispiel für diese Monomergruppe ist y-Methacryloylxypropyltriethoxysilan. Als ethylenisch ungesättigter Oxiranabkömmling kommt bevorzugt Glycidylmethacrylat und Glycidylacrylat in Betracht.Further preferred silanes are those of the general formula CH 2 = CZ-COO-Y-Si (OX) 3 , where Z is hydrogen, a methyl or ethyl group, Y is a linear or branched alkylene chain having 2 to 6 C atoms and X is represents hydrogen, an acyl group and / or an alkyl group having a maximum of 10 carbon atoms. An example of this monomer group is y-methacryloyl-oxypropyltriethoxysilane. Preferred ethylenically unsaturated oxirane derivative is glycidyl methacrylate and glycidyl acrylate.

Als sonstige Monomere f) verwendet man zum Beispiel copolymerisierbare Emulgatoren und Costabilisatoren wie Poly(alkoxylat)(meth)acrylatphosphate oder Poly(alkoxylat)(meth)acrylatalkohole oder- ether wie Plex® 6850-0, 2-(2-Methylpropenoato)ethylsulfonat oder -sulfat, Vinylsulfonat sowie funktionelle Monomere wie (Meth)acrylate mit fluoriertem Alkylrest.Other monomers f) used are, for example, copolymerizable emulsifiers and costabilizers, such as poly (alkoxylate) (meth) acrylate phosphates or poly (alkoxylate) (meth) acrylate alcohols or ethers, such as Plex® 6850-0, 2- (2-methylpropenoato) ethylsulfonate or sulfate, vinyl sulfonate and functional monomers such as fluorinated alkyl (meth) acrylates.

Als Komponenten B) kommen Benzophenon, Acetophenon und besonders Benzophenonderivate wie 1-Hydroxycyclohexylphenylketon und weiterhin 4-Methylbenzophenon sowie 2,4,6-Trimethylbenzophenon in Betracht. Vorteilhafterweise werden auch Phosphinoxidderivate, wie 2,4,6-Trimethylbenzoyldiphenylphosphinoxid alleine oder in Abmischungen mit anderen UV-Initiatoren eingesetzt. Geeignete Photoinitiatoren können auch zusammen mit Lichtstabilisatoren eingesetzt werden. Die Komponente B) wird durch Einrühren in die wenigstens ein Copolymerisat A) enthaltende wässrige Copolymerisatdispersion eingearbeitet. In der Komponente B) können Hilfsstoffe zugegeben sein, die den Photoinitiator in flüssigem Aggregatzustand halten, wie zum Beispiel Lösungsmittel oder Kristallisationsinhibitoren. Anwendungstechnisch ist es besonders vorteilhaft, wenn die Komponente B) flüssig vorliegt, da sie so leichter in die Copolymerisatdispersion einzuarbeiten ist. Die Komponente B) kann in die erfindungsgemäße Copolymerisatdispersion eingetragen werden oder alternativ dazu auch direkt in die aus der erfindungsgemäßen Copolymerisatdispersion hergestellten Beschichtung.Suitable components B) include benzophenone, acetophenone and, in particular, benzophenone derivatives such as 1-hydroxycyclohexylphenyl ketone and also 4-methylbenzophenone and 2,4,6-trimethylbenzophenone. Advantageously, phosphine oxide derivatives, such as 2,4,6-Trimethylbenzoyldiphenylphosphinoxid be used alone or in admixtures with other UV initiators. Suitable photoinitiators can also be used together with light stabilizers. Component B) is incorporated by stirring into the copolymer dispersion containing at least one copolymer A). In component B), adjuvants may be added which keep the photoinitiator in a liquid state, such as, for example, solvents or crystallization inhibitors. In terms of application, it is particularly advantageous if component B) is liquid, since it is easier to incorporate into the copolymer dispersion. Component B) can be introduced into the copolymer dispersion according to the invention or, alternatively, directly into the coating produced from the copolymer dispersion according to the invention.

Als Emulgatoren C) können solche Emulgatoren nachträglich zugesetzt werden, die auch in der Emulsionspolymerisation Verwendung finden. Als nicht ionische Emulgatoren werden beispielsweise Fettalkoholpolyalkoxylatether wie Ethoxylierungsprodukte von Lauryl-, Oleyl- oder Stearyl- sowie Kokosfettalkohol, ethoxyliertes Polypropylenoxid, poly- oder oligoethoxylierte Alkylphenole eingesetzt.As emulsifiers C) such emulsifiers can be added subsequently, which are also used in the emulsion polymerization. As nonionic emulsifiers, for example fatty alcohol polyalkoxylate ethers such as ethoxylation of lauryl, oleyl or stearyl and coconut fatty alcohol, ethoxylated polypropylene oxide, poly- or oligoethoxylierte alkylphenols are used.

Als ionische Emulgatoren können beispielsweise Alkyl-, Aryl- sowie Alkylarylsulfonate, -sulfate, -phosphonate, -phosphate oder Substanzen mit anderen anionischen oder kationischen Endgruppen verwendet werden. Zwischen der ionischen polaren Kopfgruppe und der unpolaren Einheit des Emulgators können auch Oligo- oder Polyalkylenoxideinheiten eingefügt sein.Examples of ionic emulsifiers which can be used are alkyl, aryl and alkylaryl sulfonates, sulfates, phosphonates, phosphates or substances having other anionic or cationic end groups. It is also possible to introduce oligo- or polyalkylene oxide units between the ionic polar head group and the nonpolar unit of the emulsifier.

Typische ionische Emulgatoren, die in erfindungsgemäßen Dispersionen Verwendung finden können, sind beispielsweise Natriumlaurylsulfat, Natriumlauryldi- und -triglycolethersulfat, Natriumundecylheptaglykolethersulfat, Tri(sec-butyl)phenylheptaglycolethersulfat, Natriumdodecylbenzolsulfonat sowie bevorzugt die Alkalimetall- oder Ammoniumsalze von Fettalkoholpolyglykolethersulfosuccinaten wie Aerosol® A 102 der Firma Cytec oder Disponil ® SUS 87 Spezial IS der Firma Cognis.Typical ionic emulsifiers which can be used in dispersions according to the invention are, for example, sodium lauryl sulfate, sodium lauryl di- and triglycol ether sulfate, sodium undecyl heptaglycol ether sulfate, tri (sec-butyl) phenyl heptaglycol ether sulfate, sodium dodecylbenzenesulfonate and preferably the alkali metal or ammonium salts of fatty alcohol polyglycol ether sulfosuccinates such as Aerosol® A 102 from Cytec or Disponil® SUS 87 Spezial IS from Cognis.

Als wasserlösliche Copolymerisate D) werden bevorzugt Styrol-Maleinsäureanhydrid-Copolymerisate mit einem Molekulargewicht von 1000 bis 4000 g/mol, die ganz oder teilweise mit Ammoniumhydroxid oder Alkalimetalhydroxiden neutralisiert vorliegen, nachträglich zugesetzt. Gegebenenfalls können auch modifizierte Styrol-Maleinsäureanhydrid Copolymerisate (SMA® -Harze) sowie deren Partialester eingesetzt werden. Die SMA® -Harze sollen jedoch keine mit den Cyclohexylepoxysilanen reaktiven Aminogruppen enthalten. Die Modifizierung des SMA® -Harzes kann hierbei auch in situ erfolgen.As water-soluble copolymers D) are preferably styrene-maleic anhydride copolymers having a molecular weight of 1000 to 4000 g / mol, which are wholly or partially neutralized with ammonium hydroxide or alkali metal hydroxides, added subsequently. Optionally, modified styrene-maleic anhydride copolymers (SMA® resins) and their partial esters can be used. However, the SMA® resins should not contain amino groups reactive with the cyclohexylepoxysilanes. The modification of the SMA® resin can also be done in situ.

Die Copolymerisate A) sind nach den dem Fachmann bekannten Methoden der radikalischen Substanz-, Lösungs-, Suspensions- und Emulsionspolymerisation zugänglich, wobei die Emulsionspolymerisation das bevorzugte Herstellverfahren ist.The copolymers A) are accessible by the methods of radical substance, solution, suspension and emulsion polymerization known to the person skilled in the art, the emulsion polymerization being the preferred preparation process.

Das Copolymerisat A) wird demgemäß vorzugsweise durch Emulsionspolymerisation der Monomeren a) und b) sowie gegebenenfalls c) bis f) in wäßrigem Medium in Gegenwart von radikalbildenden Initiatoren und Emulgatoren und gegebenenfalls Schutzkolloiden, Molekulargewichtsreglern und/oder weiteren Hilfsmitteln hergestellt.The copolymer A) is accordingly preferably prepared by emulsion polymerization of the monomers a) and b) and optionally c) to f) in an aqueous medium in the presence of free-radical initiators and emulsifiers and optionally protective colloids, molecular weight regulators and / or other auxiliaries.

Als Schutzkolloide in der Emulsionspolymerisation sind besonders Carboxymethylcellulosen mit einem niedrigen Molekulargewicht, wie die kommerziell verfügbaren Produkte Blanose© 7M, Blanose® 7UL und Blanose® TEL der Firma Clariant GmbH sowie Ambergum® 3021 der Firma Hercules, geeignet.Particularly suitable protective colloids in the emulsion polymerization are low molecular weight carboxymethylcelluloses, such as the commercially available products Blanose® 7M, Blanose® 7UL and Blanose® TEL from Clariant GmbH, and Ambergum® 3021 from Hercules.

Gegebenenfalls ist die Carboxymethylcellulose noch mit zusätzlichen Resten modifiziert wie mit Hydroxyalkyl- oder Alkylgruppen. Bei Bedarf können auch alkyloxyalkylmodifizierte Carboxymethylcellulosen eingesetzt werden.Optionally, the carboxymethylcellulose is still modified with additional radicals as with hydroxyalkyl or alkyl groups. If required, it is also possible to use alkyloxyalkyl-modified carboxymethylcelluloses.

Bevorzugt erfolgt die Polymerisation unter Dosierung einer Monomerenemulsion, jedoch kann sie auch nach dem Batch-, Monomerenzulauf- oder sog. Power-feed-Verfahren hergestellt werden. Bei letzterem werden die Monomere als solche oder in Monomeremulsion mit einem Gradienten in der Monomerenzusammensetzung eindosiert.Preferably, the polymerization is carried out by metering a monomer emulsion, but it can also be prepared by the batch, monomer feed or so-called power feed process. In the latter case, the monomers are metered in as such or in monomer emulsion with a gradient in the monomer composition.

Gegebenenfalls können mehrere verschiedene Monomeremulsionen eindosiert werden und damit auch morphologisch heterogene Copolymerisate erzeugt werden.Optionally, several different monomer emulsions can be metered in and thus also morphologically heterogeneous copolymers are produced.

Das oder die Schutzkolloide kann/können ganz oder zum Teil im Reaktor vorgelegt werden oder aber mit der Monomerenemulsion bzw. mit den Monomeren zudosiert werden.The protective colloid (s) may be introduced in whole or in part in the reactor or else be metered in with the monomer emulsion or with the monomers.

Zur Initiierung der Emulsionspolymerisation werden wasser- und/oder öllösliche Initiatoren eingesetzt. Die Emulsionspolymerisation kann hierbei durch thermische Zersetzung des Initiators oder durch Redoxpolymerisation eingeleitet und aufrechterhalten werden. In letzterem Falle kann die Reaktion sogar bei Temperaturen unterhalb oder bei Raumtemperatur durchgeführt werden.Water and / or oil-soluble initiators are used to initiate the emulsion polymerization. The emulsion polymerization can be initiated and maintained by thermal decomposition of the initiator or by redox polymerization. In the latter case, the reaction can be carried out even at temperatures below or at room temperature.

Üblicherweise wird die Emulsionspolymerisation bei Reaktortemperaturen zwischen 50 und 85°C durchgeführt.Usually, the emulsion polymerization is carried out at reactor temperatures between 50 and 85 ° C.

Geeignete Initiatoren sind z.B. Wasserstoffperoxid, Kalium-, Natrium- oder Ammoniumperoxodisulfat, t-Butylhydroperoxid, Laurylhydroperoxid, Dibenzoylperoxid sowie andere Organoperoxide. Alternativ kann die Polymerisation auch in Gegenwart von zusätzlich einer oder mehreren reduzierenden Substanzen wie Natriummetabisulfit, Rongalit® , Ascorbinsäure, Glucose durchgeführt werden (Redoxpolymerisation). Bei der Redoxpolymerisation werden bevorzugt katalytisch wirkende Metallsalze wie Eisen(III)chlorid zugesetzt, um die Radikalbildung zu beschleunigen.Suitable initiators are e.g. Hydrogen peroxide, potassium, sodium or ammonium peroxodisulfate, t-butyl hydroperoxide, lauryl hydroperoxide, dibenzoyl peroxide and other organoperoxides. Alternatively, the polymerization can also be carried out in the presence of one or more reducing substances such as sodium metabisulfite, Rongalit®, ascorbic acid, glucose (redox polymerization). In the redox polymerization catalytically active metal salts such as iron (III) chloride are preferably added to accelerate the formation of radicals.

Zur Steuerung des Molekulargewichts können während der Emulsionspolymerisation Regler eingesetzt werden, wie Mercaptane, insbesondere n-Dodecylmercaptan, Thiophenol oder Alkohole. Übliche Zusatzmengen des Reglers bewegen sich zwischen 0,05 und 0,3 Gew. %, bezogen auf das Gesamtgewicht des Copolymerisats.To control the molecular weight, it is possible during the emulsion polymerization to use regulators, such as mercaptans, in particular n-dodecyl mercaptan, thiophenol or alcohols. Usual additional amounts of the regulator are between 0.05 and 0.3% by weight, based on the total weight of the copolymer.

Üblicherweise werden die erfindungsgemäßen Dispersionen auf einen pH-Wert von 3 bis 10 mit einer oder mehreren Basen eingestellt. Die pH-Werteinstellung kann auch durch Neutralisation der Monomeremulsion und/oder Vorlage mit Basen vor der Polymerisation erfolgen. Vorzugsweise wird der pH-Wert der Vorlage und/oder Monomeremulsion auf einen Wert >= 2,5 eingestellt. Besonders bevorzugt liegt der pH -Wert der Vorlage bei einem Wert >= 2,5 und der pH-Wert der Monomeremulsion bei einem pH-Wert >= 4. Besonders bevorzugt wird der pH-Bereich der Vorlage auf pH >= 2,5 und <= 7 und derjenige der Monomeremulsion auf >= 4 und <= 7 eingestellt.Usually, the dispersions of the invention are adjusted to a pH of 3 to 10 with one or more bases. The pH adjustment can also be carried out by neutralization of the monomer emulsion and / or base with bases prior to the polymerization. Preferably, the pH of the template and / or monomer emulsion is adjusted to a value> = 2.5. Particularly preferably, the pH of the template is at a value> = 2.5 and the pH of the monomer emulsion at a pH> = 4. Particularly preferably, the pH range of the template to pH> = 2.5 and <= 7 and that of the monomer emulsion is set to> = 4 and <= 7.

Alternativ dazu kann der pH-Wert des Monomerzulaufs im Falle der Anwendung des Monomerzulaufverfahrens durch Dosierung der in wäßriger Lösung oder Suspension vorliegenden und (teil)neutralisierten (Meth)acrylsäure eingestellt werden.Alternatively, if the monomer feed process is used, the pH of the monomer feed may be adjusted by dosing the (partially) neutralized (meth) acrylic acid present in aqueous solution or suspension.

Durch diese Maßnahmen werden die Koagulatbildung während der Emulsionspolymerisation zurückgedrängt, andererseits sind in der Emulsionspolymerdispersion anwesende Oxiran- und Alkoxysilangruppen bei einem pH-Bereich zwischen 4 und 7 gegenüber Hydrolyse stabiler als im sauren oder alkalischen Milieu. Bevorzugt werden als Basen zur pH-Werteinstellung Ammoniak-, Alkalimetall- und/oder Erdalkalihydroxid- sowie Natriumcarbonatlösungen eingesetzt. Alternativ dazu können auch andere Pufferlösungen oder Basen eingesetzt werden. Weiterhin können den erfindungsgemäßen Copolymerisatdispersionen noch Koaleszenzmittel, wie Testbenzin, Texanol, Butyldiglykol, Weichmacher, wie Dimethylphthalat und Dibutylphthalat, Verdicker basierend auf Polyacrylaten und/oder Polyurethanen zugesetzt werden. Beispiele für geeignete Verdicker sind Borchigel® L 75 N der Firma Borchers, Tafigel® PUR 40 der Firma Münzing-Chemie, DSX® 1550 der Firma Cognis.On the other hand, oxirane and alkoxysilane groups present in the emulsion polymer dispersion are more stable to hydrolysis at a pH range between 4 and 7 than in an acidic or alkaline medium. Ammonium, alkali metal and / or alkaline earth metal hydroxide and sodium carbonate solutions are preferably used as bases for pH adjustment. Alternatively, other buffer solutions or bases may be used. Furthermore, coalescing agents, such as white spirit, Texanol, butyldiglycol, plasticizers, such as dimethyl phthalate and dibutyl phthalate, thickeners based on polyacrylates and / or polyurethanes may also be added to the novel copolymer dispersions. Examples of suitable thickeners are Borchigel® L 75 N from Borchers, Tafigel® PUR 40 from Münzing-Chemie, DSX® 1550 from Cognis.

Konservierungsmittel, Entschäumer, Netzmittel, UV-Stabilisatoren, Korrosionsschutzinhibitoren und -pigmente, anorganische Silicakolloiddispersionen, Füllstoffe, Pigmente und andere Zusätze, die dem Fachmann zur Herstellung von Beschichtungszusammensetzungen bekannt sind, können ebenfalls zugesetzt werden.Preservatives, defoamers, wetting agents, UV stabilizers, anticorrosion inhibitors and pigments, inorganic silica colloid dispersions, fillers, pigments and other additives known to those skilled in the art for preparing coating compositions may also be added.

Die erfindungsgemäßen wässrigen Copolymerisatdispersionen sind besonders geeignet zur Verwendung in elastischen Fassadenfarben und Dachbeschichtungen, Dichtmassen und Dichtschlämmen, Bindemitteln für Lederfasern und in Klebstoffen. Die Zubereitungen zeichnen sich durch sehr gute Rückstellkraft nach Dehnung der Beschichtungen aus.The novel aqueous copolymer dispersions are particularly suitable for use in elastic facade paints and roof coatings, sealants and sealing slurries, binders for leather fibers and in adhesives. The preparations are characterized by very good restoring force after stretching of the coatings.

Die vorliegende Erfindung wird im folgenden anhand von Ausführungsbeispielen näher beschrieben, ohne jedoch dadurch beschränkt zu werden.The present invention will be described in more detail below with reference to exemplary embodiments, without, however, being restricted thereby.

Bestimmung der Reißdehnung und Zugspannung:Determination of elongation at break and tensile stress:

Filme der zu prüfenden Beschichtungen wurden mit einem 400 µm-Kastenrakel auf eine Polyethylenfolie aufgezogen und bei 23°C und 50% relativer Luftfeuchte 7 Tage gelagert. Dann wurden mit einer Stanze 6 Probekörper pro Beschichtung mit den Maßen 110mm*15 mm ausgelöst und die Dicke der Beschichtungsprüfkörper mit einem Schichtdickenmeßgerät Deltascope der Firma Fischer ermittelt und notiert. Sodann wurden die Filme in eine Zugprüfmaschine Typ 4302 der Firma Instron mit 100N-Kraftmeßdose und handelsüblicher PC-Steuerung eingespannt. Hierbei betrug die freie Filmlänge zwischen den Klemmbacken 60 mm. Dann wurde mit einer Zuggeschwindigkeit von 200mm/min bis zum Filmriß gedehnt. Das PC-Programm erfaßt die (Reiß)dehnung und die Zugspannung bis zum Filmriß, weiterhin das Young-Modul sowie die Bruchenergieaufnahme. Für die Ermittlung dieser Daten muß vor dem Versuch die Trockenfilmdicke im PC-Programm eingegeben werden.Films of the coatings to be tested were coated on a polyethylene film with a 400 μm doctor blade and kept at 23 ° C. and 50% relative humidity for 7 days stored. Then 6 test specimens per coating with the dimensions 110 mm * 15 mm were triggered with a punch and the thickness of the coating test specimens was determined with a Deltascope coating thickness meter from Fischer and noted. The films were then clamped in a Instron type 4302 tensile testing machine with 100N load cell and commercial PC control. Here, the free film length between the jaws was 60 mm. Then it was stretched at a pulling speed of 200mm / min until the film broke. The PC program detects the (tear) elongation and the tensile stress up to the film break, furthermore the Young's module as well as the breakage energy absorption. To determine these data, the dry film thickness must be entered in the PC program before the test.

Bestimmung der Teilchengröße:Determination of particle size:

Die Partikelgröße der Polymerdispersionen wurde mittels Photonenkorrelationsspektroskopie bei einem Streuwinkel von 90° als Gewichtsmittel (dw) ermittelt.The particle size of the polymer dispersions was determined by means of photon correlation spectroscopy at a scattering angle of 90 ° as the weight average (d w ).

Beispiel 1example 1 Herstellung einer wäßrigen CopolymerisatdispersionPreparation of an aqueous copolymer dispersion

500g n-Butylacrylat, 200g 2-Ethylhexylacrylat, 270g Styrol und 20g Methacrylsäure (Monomerenmischung) wurden in eine Lösung aus 64,4g Genapol® LRO mit einem Gehalt von 28 Gew. % Laurylalkoholdiglykolethersulfat-Natriumsalz als Aktivsubstanz in Wasser (von der Firma Clariant) und 954 g Wasser emulgiert und die Emulsion noch 10 Minuten bei 1000 Umdrehungen pro Minute (UpM) mit einem Dissolver geschert.500 g of n-butyl acrylate, 200 g of 2-ethylhexyl acrylate, 270 g of styrene and 20 g of methacrylic acid (monomer mixture) were dissolved in a solution of 64.4 g of Genapol® LRO containing 28% by weight of lauryl alcohol diglycol ether sulfate sodium salt as active substance in water (from Clariant). and emulsified 954 g of water and sheared the emulsion for 10 minutes at 1000 revolutions per minute (rpm) with a dissolver.

Davon wurden 202 g Monomeremulsion abgewogen und mit einer Lösung aus 0,5g Natriumperoxodisulfat in 10g Wasser versetzt. Sodann wurde diese Vorlage in einem Glasreaktor unter Rühren (120 UpM, Ankerrührer) auf 80°Caufgeheizt und nach 10 min. Warten die restliche Monomeremulsion binnen 2,5 h durch einen Tropftrichter zudosiert. Parallel zur Monomeremulsion wurde eine Lösung aus 4,3g Natriumperoxodisulfat und 90g Wasser zum Ansatz durch einen Tropftrichter zugegeben. Nach Zulaufende wurde noch 1 h bei 80°C nachgeheizt, sodann wurde beim Abkühlen der Ansatz bei ca. 70°C mit 12,5 Gew. %-igem Ammoniakwasser auf einen pH-Wert von 7 eingestellt. Abschließend wurden bei 25°C Innentemperatur 7g Irgacure 500 der Firma Ciba Specialty Chemicals in die Dispersion eingerührt. Man erhielt eine Copolymerisatdispersion mit einem Feststoffgehalt von ca. 48 Gew. %. Die Teilchengröße dw betrug 138 nm.Of these, 202 g of monomer emulsion were weighed and treated with a solution of 0.5 g of sodium peroxodisulfate in 10 g of water. Then this template was heated to 80 ° C in a glass reactor with stirring (120 rpm, anchor agitator) and after 10 min. Wait for the remaining monomer emulsion within 2.5 h metered through a dropping funnel. Parallel to the monomer emulsion was a solution of 4.3 g Sodium peroxodisulfate and 90 g of water added to the beginning through a dropping funnel. After the end of the feed was further heated at 80 ° C for 1 h, then the mixture was adjusted to a pH of 7 at about 70 ° C with 12.5 wt.% Ammonia water on cooling. Finally, 7 g of Irgacure 500 from Ciba Specialty Chemicals were stirred into the dispersion at 25 ° C. internal temperature. A copolymer dispersion having a solids content of about 48% by weight was obtained. The particle size dw was 138 nm.

Beispiel 2Example 2

Als Copolymerisatdispersion wurde eine UV-vernetzende Acrylatdispersion für Elastbeschichtungen mit einem Gehalt an ca. 55 Gew. % Mowilith® LDM 7900 der Firma Celanese Emulsions GmbH verwendet.The copolymer dispersion used was a UV-crosslinking acrylate dispersion for elastomeric coatings containing about 55% by weight of Mowilith® LDM 7900 from Celanese Emulsions GmbH.

Beispiel 3Example 3 Herstellung der erfindungsgemäßen Cyclohexylepoxysilan haltigen wässrigen CopolymerisatePreparation of the cyclohexylepoxysilane-containing aqueous copolymers according to the invention

In die Copolymerisatdispersionen des Beispiels 1 und 2 wurde das Cyclohexylepoxysilan Coatosil® 1770 (OSi, entsprechend β-(3,4-Epoxycyclohexyl)-ethyltriethoxysilan)] mit einem mechanischen Rührer eingearbeitet und durch 10 min. Rühren in der Dispersion gleichmäßig verteilt. Tabelle 1: Beispiel Dispersion Gewichts-% β-(3,4-Epoxycyclohexyl)ethyl triethoxysilan), bezogen auf die wässrige Dispersion 3a (Vergleich) Beispiel 1 - 3b Beispiel 1 0,1 3c (Vergleich) Beispiel 2 - 3d Beispiel 2 0,1 In the copolymer dispersions of Examples 1 and 2, the cyclohexylepoxysilane Coatosil® 1770 (OSi, corresponding to β- (3,4-epoxycyclohexyl) ethyltriethoxysilane)] was incorporated with a mechanical stirrer and by 10 min. Stir evenly in the dispersion. Table 1: example dispersion % By weight of β- (3,4-epoxycyclohexyl) ethyltriethoxysilane), based on the aqueous dispersion 3a (comparative) example 1 - 3b example 1 0.1 3c (comparison) Example 2 - 3d Example 2 0.1

Beispiel 4Example 4 Herstellung von elastischen FassadenbeschichtungenProduction of elastic facade coatings

In 100 g Wasser wurden unter Rühren nacheinander 5 g einer 10 %-igen Lösung von Calgone N der Firma BK Ladenburg und 1,4 g Coatex® P 90 der Firma Dimed sowie 2 g Foammaster® 111 FA der Firma Cognis zugegeben. Dann wurden 80 g Titandioxid (Kronos® L 2310, der Firma Kronos Titan) und 380 g Calciumcarbonat (Durcal® 2, der Firma Omya) nacheinander zugegeben und mit einem Dissolver 15 Minuten bei 5000 UpM gerührt. Anschließend wurden 485 g (Beispiel 3a, b) bzw. 422 g (Beispiel 3c, d) Polymerdispersion bei 500 UpM sowie 1 g 25 %-iges Ammoniakwasser zugegeben und 5 Minuten gerührt. Schließlich gab man 2 g Mergal® K9 der Firma Troy, 2 g Butyldiglykol, 10 g Propylenglykol, 5 g Testbenzin (Siedebereich 135-180°C) und abschließend eine Lösung aus 7,5 g Coatex® BR 100 der Firma Dimed und 23,2 g Wasser hinzu. Anschließend wurde noch ca. 5 Minuten weitergerührt. Tabelle 2: Beispiel Dispersion Additiv [Gew. %, bezogen auf die wässrige Dispersion] 4a (Vergleich) Beispiel 1 - 4b Beispiel 1 0,1 4c (Vergleich) Beispiel 2 - 4d Beispiel 2 0,1 5 g of a 10% solution of Calgone N from BK Ladenburg and 1.4 g of Coatex® P 90 from Dimed and 2 g of Foammaster® 111 FA from Cognis were added in succession to 100 g of water with stirring. Then, 80 g of titanium dioxide (Kronos® L 2310, from Kronos Titan) and 380 g of calcium carbonate (Durcal® 2, from Omya) were added successively and stirred with a dissolver for 15 minutes at 5000 rpm. Subsequently, 485 g (Example 3a, b) or 422 g (Example 3c, d) polymer dispersion at 500 rpm and 1 g of 25% ammonia water was added and stirred for 5 minutes. Finally, 2 g of Mergal® K9 from Troy, 2 g of butyldiglycol, 10 g of propylene glycol, 5 g of white spirit (boiling range 135-180 ° C.) and finally a solution of 7.5 g of Coatex® BR 100 from Dimed and 23, Add 2 g of water. The mixture was then stirred for about 5 minutes. Table 2: example dispersion Additive [wt. %, based on the aqueous dispersion] 4a (comparison) example 1 - 4b example 1 0.1 4c (comparison) Example 2 - 4d Example 2 0.1

Beispiel 5Example 5 Bestimmung der Reißdehnung und Zugspannung von BeschichtungenDetermination of the elongation at break and tensile stress of coatings

Tabelle 3:Table 3: Beschichtungcoating Zugspannung beim Bruch [MPa]Tensile stress at break [MPa] Reißdehnung beim Bruch [%]Elongation at break [%] D Reißdehnung [%]D elongation at break [%] Bruchenergie [J]Fracture energy [J] D Bruchenergie [%]D fracture energy [%] 4a (Vergleich)4a (comparison) 1,021.02 360360 0,430.43 4b4b 1,041.04 524524 +45.6+45.6 0,790.79 83,783.7 4c (Vergleich)4c (comparison) 1,361.36 139139 0,220.22 4d4d 1,391.39 161161 +15.8+15.8 0,270.27 22,722.7

Wie ein Vergleich der Beispiele 4a mit 4b und 4c mit 4d zeigt, zeichnen sich die Beschichtungen 4b und 4d, die auf den erfindungsgemäßen Cyclohexylepoxisilan haltigen Copolymerisaten basieren, durch eine erhöhte Zugspannung und damit erhöhte Rückstellkraft nach der Dehnung der Beschichtung aus.As a comparison of Examples 4a with 4b and 4c with 4d shows, the coatings 4b and 4d, which are based on the cyclohexylepoxisilan copolymers according to the invention, characterized by an increased tensile stress and thus increased restoring force after the elongation of the coating.

Claims (26)

  1. An aqueous copolymer dispersion obtainable by free-radical polymerization at least of monomers a) and b) and by subsequent addition of at least one cycloalkylepoxysilane to the resulting copolymer emulsion, monomer a) being an ester of α,β-monoethylenically unsaturated carboxylic acids containing 3 to 6 carbon atoms and alkanols containing 1 to 18 carbon atoms and, if desired, a vinylaromatic compound, or a mixture of these monomers, and monomer b) being a monobasic or polybasic α,β-monoethylenically unsaturated acid and/or anhydride thereof.
  2. The aqueous copolymer dispersion as claimed in claim 1, wherein in addition to monomers a) and b) use is also made of at least one of the monomers c), d), e) and/or f), monomer c) being a diethylenically or oligoethylenically unsaturated crosslinking monomer or a mixture of these monomers, monomer d) being an α,β-monoethylenically unsaturated carboxamide containing 3 to 8 carbon atoms, or a mixture of these monomers, monomer e) being a reactive crosslinker monomer selected from a combination of at least one ethylenically unsaturated silane with at least one ethylenically unsaturated monomer containing an oxirane group, or a mixture of these monomers, and monomer f) being another kind of copolymerizable ethylenically unsaturated monomer or a mixture of these monomers, with the exception of a nitrogen-containing monomer which is reactive with epoxy groups.
  3. The aqueous copolymer dispersion as claimed in claim 1, which has a solids content of 20 - 65% by weight, and wherein the copolymer is derived from 40 to 99.8% by weight of monomer a) or mixtures thereof, from 0.1 to 10% by weight of monomer b) or mixtures thereof, from 0 to 10% by weight of monomer c) or mixtures thereof, from 0 to 5% by weight of monomer d) or mixtures thereof, from 0 to 5% by weight of monomer e) or mixtures thereof, and from 0 to 30% by weight of monomer f) or mixtures thereof, the amounts of monomer being based on the total amount of monomer employed.
  4. The aqueous copolymer dispersion as claimed in claim 1, wherein within the limits described the weight fractions of the monomers a) and b) are chosen such that a copolymer synthesized only from these monomers would have a glass transition temperature in the range between -50 to 120°C.
  5. The aqueous copolymer dispersion as claimed in claim 1, wherein the cycloalkylepoxysilane is a compound of the general formula (I)
    Figure imgb0006
     where R1, R2, and R3 are linear or branched alkoxy radicals with the oxygen atom bonding to the silicon atom and/or are alkyl radicals having 1-10 carbon atoms and R4 is a linear or branched alkylene radical having1-10 carbon atoms.
  6. The aqueous copolymer dispersion as claimed in claim 1, comprising one or more UV initiators B) and/or one or more emulsifiers C), and/or one or more water-soluble copolymers D).
  7. The aqueous copolymer dispersion as claimed in claim 1, which has a solids content of 20 - 65% by weight and is obtainable by preparing a copolymer A) consisting essentially of
    a) from 40 to 99.8% by weight, of at least one ester of α,β-monoethylenically unsaturated carboxylic acids containing from 3 to 6 carbon atoms and alkanols containing 1 to 18 carbon atoms, and from 0 to 30% by weight of at least one vinylaromatic compound (monomers a),
    b) from 0.1 to 10% by weight of at least one monobasic or polybasic α,β-monoethylenically unsaturated acid or anhydrides thereof (monomers b),
    c) from 0 to 10% by weight of at least one diethylenically or oligoethylenically unsaturated crosslinking monomer (monomers c),
    d) from 0 to 5% by weight of at least one α,β-monoethylenically unsaturated carboxamide which contains 3 to 8 carbon atoms and may be substituted once or twice on the nitrogen by alkylene groups containing up to 5 carbon atoms, alkyl sulfates, alkylsulfonates, alkyl phosphates, alkyl ethers or alkyl ether sulfates or alkyl ether phosphates (monomers d),
    e) from 0 to 5% by weight of reactive crosslinker monomers selected from a combination of at least one ethylenically unsaturated silane with at least one ethylenically unsaturated monomer containing an oxirane group (monomers e),
    f) from 0 to 30% by weight of at least one other kind of copolymerizable ethylenically unsaturated monomer (monomers f), with the exception of nitrogen-containing monomers which are reactive with epoxy groups,
    the weight fractions being based on the total weight of monomers, and the weight fractions of the monomers a) and b) being chosen within the limits described such that a copolymer synthesized only from these monomers would have a glass transition temperature in the range between -50 and 15°C;
    by polymerizing the monomers a) to f) in water, and subsequently adding to the resultant aqueous copolymer dispersion one or more functional cyclohexylepoxysilanes of the general formula (I)
    Figure imgb0007
     where R1, R2, and R3 are linear or branched alkoxy radicals with the oxygen atom bonding to the silicon atom and/or are alkyl radicals having 1-10 carbon atoms and R4 is a linear or branched alkylene radical having 1-10 carbon atoms, at temperatures between 25 and 90°C;
    and subsequently adding, if desired, one or more UV initiators B) in an amount of from 0 to 5% by weight, based on the copolymer A);
    if desired, one or more emulsifiers C), in an amount of from 0 to 10% by weight, based on the copolymer A); and
    if desired, one or more water-soluble copolymers D), in an amount of from 0 to 4% by weight, based on the copolymer A),
    to the aqueous copolymer dispersion.
  8. The aqueous copolymer dispersion as claimed in claim 7, wherein the cyclohexylepoxysilane of the general formula (I) is added in an amount of up to 1 % by weight, based on the aqueous dispersion of the copolymer A).
  9. The aqueous copolymer dispersion as claimed in claim 7, wherein the radicals R1, R2, and R3 in the general formula (I) in each case independently of one another are -OCH3 or -OC2H5 and the radical R4 is -C2H4-.
  10. The aqueous copolymer dispersion as claimed in claim 7, wherein as esters of α,β-monoethylenically unsaturated carboxylic acids containing 3 to 6 carbon atoms and alkanols containing 1 to 18 carbon atoms esters of acrylic acid and/or methacrylic acid are used.
  11. The aqueous copolymer dispersion as claimed in claim 7, wherein as vinylaromatic compound styrene is used.
  12. The aqueous copolymer dispersion as claimed in claim 7, wherein as α,β-monoethylenically unsaturated carboxamide methacrylamide is used.
  13. The aqueous copolymer dispersion as claimed in claim 7, wherein as monomers e) silanes of the general formula CH2=CH-Si(OX)3 are used where X is hydrogen, an acyl group or an alkyl group having not more than ten carbon atoms.
  14. The aqueous copolymer dispersion as claimed in claim 7, wherein as monomers e) silanes of the general formula CH2=CZ-COO-Y-Si(OX)3 are used where Z is hydrogen or a methyl or ethyl group, Y is a linear or branched alkylene chain having 2 to 6 carbon atoms, and X is hydrogen, an acyl group or an alkyl group having not more than ten carbon atoms.
  15. The aqueous copolymer dispersion as claimed in claim 7, wherein as monomers e) glycidyl methacrylate and/or glycidyl acrylate are used.
  16. The aqueous copolymer dispersion as claimed in claim 7, wherein as component B) benzophenone, acetophenone, 1-hydroxycyclohexyl phenyl ketone, 4-methylbenzophenone and 2,4,6-trimethylbenzophenone are used.
  17. The aqueous copolymer dispersion as claimed in claim 7, wherein as component C) nonionic and/or ionic emulsifiers are used.
  18. The aqueous copolymer dispersion as claimed in claim 7, wherein as water-soluble copolymer D) styrene-maleic anhydride copolymers having a molecular weight of from 1000 to 4000 g/mol are used.
  19. A process for preparing an aqueous copolymer dispersion as claimed in claim 1, which comprises subjecting the monomers a) and b) and, where appropriate, c), d), e) and/or f) as set forth in claim 2 to free-radical polymerization in aqueous medium in the presence of water-soluble radical-forming initiators, emulsifiers and/or protective colloids, regulators and/or further auxiliaries, by emulsion polymerization, and subsequently adding to the resulting aqueous copolymer dispersion one or more cycloalkylepoxysilanes, at temperatures between 25 and 90°C, and subsequently adding, if desired, one or more UV initiators B), if desired, one or more emulsifiers C), and, if desired, one or more water-soluble copolymers D).
  20. A process for preparing an aqueous copolymer dispersion as claimed in claim 19, wherein a compound of the formula (I) is used as cycloalkylepoxysilane
    Figure imgb0008
     where R1, R2, and R3 are linear or branched alkoxy radicals with the oxygen atom bonding to the silicon atom and/or are alkyl radicals having 1-10 carbon atoms and R4 is a linear or branched alkylene radical having 1-10 carbon atoms.
  21. The use of the aqueous copolymer dispersion as claimed in claim 1 for producing coatings.
  22. The use as claimed in claim 21 for elastic masonry paints and elastic roof coatings.
  23. The use of the aqueous copolymer dispersion as claimed in claim 1 for grouts.
  24. The use of the aqueous copolymer dispersion as claimed in claim 1 as a leather fiber binder.
  25. The use of the aqueous copolymer dispersion as claimed in claim 1 for adhesives.
  26. A coating material comprising an aqueous copolymer dispersion as claimed in claim 1 and substantially
    a) pigments,
    b) fillers,
    c) dispersants,
    d) wetting agents,
    e) UV filter substances,
    f) flame retardants,
    g) thickeners,
    h) plasticizers, and
    i) defoamers.
EP04009362A 2003-05-28 2004-04-21 Aqueous copolymer dispersions, method for their production and coating compositions containing them Expired - Lifetime EP1481995B1 (en)

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